CN113593917A - Synthesis method of cellular three-dimensional graphene and application of cellular three-dimensional graphene in quasi-solid-state dye-sensitized solar cell - Google Patents
Synthesis method of cellular three-dimensional graphene and application of cellular three-dimensional graphene in quasi-solid-state dye-sensitized solar cell Download PDFInfo
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Abstract
The invention discloses a synthesis method of cellular three-dimensional graphene and application of the cellular three-dimensional graphene in a quasi-solid dye-sensitized solar cell, which comprises the steps of weighing graphene oxide GO in a beaker, adding distilled water, performing ultrasonic treatment until the GO is completely dissolved, adding ammonia water to adjust the pH value, transferring a mixed solution to a reaction kettle, and performing a perfect hydrothermal reaction; cooling to room temperature to obtain black reduced graphene oxide rGO solid, and centrifuging and washing; after centrifugation, firstly freezing treatment is carried out, and then freeze drying is carried out in a freeze dryer, so that the three-dimensional graphene 3D-rGO can be obtained. And preparing the quasi-solid dye-sensitized solar cell by using the three-dimensional graphene 3D-rGO. The prepared three-dimensional graphene has a loose porous structure, the specific surface area of the three-dimensional graphene is enlarged, more contact areas are provided for the contact of electrolyte and an electrolytic material, the electro-catalytic activity is higher, and the photoelectric efficiency of the prepared quasi-solid electrolyte sensitized cell is improved by 51.26%.
Description
Technical Field
The invention relates to the technical field of synthesis of nano materials and application of the nano materials in dye-sensitized solar cells. In particular to a synthesis method of honeycomb three-dimensional graphene and application thereof in a quasi-solid dye-sensitized solar cell.
Background
With the rapid development of economy and the increase of population, fossil fuels such as petroleum, natural gas and coal are exploited and used on a large scale, the consumption of non-renewable energy sources is more and more, and meanwhile, the environmental crisis is also brought, so that the development of clean and renewable energy sources is necessary to relieve the crisis problem caused by resource consumption. Biological energy, nuclear energy, ocean energy, hydrogen energy, solar energy and the like are renewable energy sources, and the energy provided by the solar energy is multiple times of the energy provided by other energy sources at most. Therefore, solar energy is a research direction in which researchers are very interested, and dye-sensitized solar cells (DSSCs) are considered to be a new development direction that can replace silicon solar cells due to their advantages of green, no pollution, high photoelectric conversion efficiency, relatively low price, and the like.
The counter electrode material of the dye-sensitized solar cell is mainly used for regenerating an oxidation-reduction couple in a catalytic electrolyte, so that high catalytic activity is required as the counter electrode material. Pt is the most common counter electrode material at present, the catalytic performance of the Pt is very excellent, and the energy conversion efficiency can be greatly improved, but the Pt is expensive and small in amount, and cannot meet the requirement of wide-range application of DSSCs. Therefore, developing a counter electrode material with good catalytic performance to replace Pt is an important direction for the current research of dye-sensitized solar cells. Compared with other types of solar cells, the dye-sensitized solar cell has price advantage, but the performance of the dye-sensitized solar cell still needs to be improved at present, and in order to further improve the photoelectric conversion efficiency of the DSSCs, scientific researchers are actively searching and researching counter electrode materials.
The carbon material has rich resource, no pollution, low cost and easy preparation, so that the carbon material can be applied in large scale. In addition, the carbon material has high stability, strong conductive capability and catalytic energyStrong force and no contact with I in electrolyte3 -/I-The advantages of the reaction and the like determine the application of the composite material in the aspect of dye-sensitized solar cells, and the composite material can be used as a material for replacing Pt as a counter electrode. The carbon materials widely researched at present comprise carbon nanotubes, carbon black, activated carbon, graphene and the like, the graphene becomes a counter electrode material with development prospect due to the advantages of excellent conductivity, large specific surface area and controllable size, the graphene can be doped with other substances to optimize the defects of the graphene when the graphene is used as a counter electrode, and if the two-dimensional structure of the graphene is transited to the three-dimensional structure, the application field of the graphene is wider. Tang et al have studied Reduced Graphene Oxide (RGO) and three-dimensional graphene networks (3D-GNs) to jointly modify DSSCs, and the results show that the photoelectric conversion efficiency reaches 7.68%, and the joint modification effect of the two is far greater than the efficiency of RGO and 3D-GNs which are independently used as counter electrode materials; ahn et al report that 3D-GNs grown by p-doped precursor assisted CVD are used as counter electrodes, and the result shows that the photoelectric conversion efficiency is as high as 8.46%; it can be seen that the three-dimensional graphene and other substance doping can obtain higher efficiency. At present, three-dimensional graphene is mostly doped with other substances, and the electrocatalytic activity of the prepared three-dimensional graphene material and the photoelectric property of a sensitized quasi-solid battery are not satisfactory.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to provide a synthesis method of honeycomb three-dimensional graphene and application of the method in a quasi-solid dye-sensitized solar cell; the three-dimensional graphene prepared by the method has a loose porous structure, the specific surface area of the three-dimensional graphene is enlarged, and the prepared quasi-solid electrolyte sensitized cell has excellent performance.
In order to solve the technical problems, the invention provides the following technical scheme:
weighing graphene oxide GO in a beaker, adding distilled water, performing ultrasonic treatment until the GO is completely dissolved, adding ammonia water to adjust the pH value, transferring the mixed solution to a reaction kettle, and performing a perfect hydrothermal reaction; cooling to room temperature to obtain black reduced graphene oxide rGO solid, and centrifuging and washing; after centrifugation, firstly freezing treatment is carried out, and then freeze drying is carried out in a freeze dryer, so that the three-dimensional graphene 3D-rGO can be obtained.
Weighing 40mg of graphene oxide GO in a beaker, adding 100mL of distilled water, performing ultrasonic treatment until the GO is completely dissolved, adding ammonia water to adjust the pH value to 10-11, transferring the mixed solution to a reaction kettle, and performing hydrothermal reaction at 180 ℃ for 20 hours; cooling to room temperature to obtain black reduced graphene oxide rGO solid, and centrifuging and washing for four times, wherein each time is 20 min; after centrifugation, the mixture is firstly frozen overnight at the temperature of minus 20 ℃, and then is frozen and dried in a freeze dryer for 60 hours, so that the three-dimensional graphene 3D-rGO can be obtained.
The application of the honeycomb three-dimensional graphene in the quasi-solid dye-sensitized solar cell comprises the following steps:
(1) manufacturing a photo-anode;
(2) manufacturing a photocathode by using the prepared three-dimensional graphene 3D-rGO;
(3) and (5) packaging the battery.
The application of the honeycomb three-dimensional graphene in the quasi-solid dye-sensitized solar cell is as follows, in the step (1):
(1-1) putting cleaned 3cm x 6cm FTO glass on a screen printer with the conductive surface facing upwards, and uniformly coating TiO on a scraper2Slurry, inclined scraper, downward force brush, TiO2The slurry permeates into the FTO glass through the small holes on the template, so that a layer of TiO is uniformly brushed on the conductive surface of the FTO glass2Heating the brushed FTO glass in a muffle furnace, and taking out after cooling; repeating the steps for 3 times until 3 layers of uniform TiO are brushed on the same position of the FTO glass2The film is thin, and the thickness of the film is 13 mu m;
(1-2) brushing with TiO2The conductive glass is heated, is put into the prepared N719 dye solution to be soaked when the conductive glass is hot, is taken out, is washed by acetonitrile, and is dried for standby.
The application of the cellular three-dimensional graphene in the quasi-solid dye-sensitized solar cell,
in the step (1-1), the inclination angle of the scraper is 45 degrees; the heating conditions in the muffle furnace are as follows: the muffle furnace was warmed to 500 ℃ over 1h and held at 500 ℃ for 1 h.
The application of the cellular three-dimensional graphene in the quasi-solid dye-sensitized solar cell,
in the step (1-2), brush with TiO2The conductive glass is heated for 1h at 140 ℃; soaking in prepared N719 dye solution for 16-18 hr; washing with acetonitrile for 3-4 times;
the preparation method of the N719 dye solution comprises the following steps: 3mg of N719 dye was dissolved in a mixed solvent of 5mL acetonitrile and 5mL t-butanol.
The application of the honeycomb three-dimensional graphene in the quasi-solid dye-sensitized solar cell is as follows, in the step (2):
preparing a three-dimensional graphene 3D-rGO turbid liquid, sucking the prepared 3D-rGO turbid liquid by using a liquid transfer gun, coating the liquid in a square pasted by an adhesive tape, drying the liquid under an infrared lamp, continuously dripping the liquid after the solution is dried, and repeating the dripping until a layer of thin material is arranged on the FTO glass; after the solution is dried, the adhesive tape is torn off, and the adhesive tape is put into a tube furnace for sintering under nitrogen atmosphere.
The application of the cellular three-dimensional graphene in the quasi-solid dye-sensitized solar cell,
the preparation method of the three-dimensional graphene 3D-rGO turbid liquid comprises the following steps: the solvent is in a volume ratio VAnhydrous ethanol:VUltrapure waterThe solute is the three-dimensional graphene 3D-rGO prepared in the above way, and the solute and the solvent are mixed to obtain a 0.4mg/mL three-dimensional graphene suspension.
When the cellular three-dimensional graphene is applied to the quasi-solid dye-sensitized solar cell, 5 mu L of the cellular three-dimensional graphene is absorbed for drop coating during first drop coating, 10 mu L of the cellular three-dimensional graphene is absorbed for drop coating from the beginning of the second drop coating, and 120 mu L of the cellular three-dimensional graphene is added dropwise; sintering for 1h in a tube furnace at 200 ℃.
The application of the honeycomb three-dimensional graphene in the quasi-solid dye-sensitized solar cell is as follows, in the step (3):
taking the photo-anode manufactured in the step (1) and the photo-cathode manufactured in the step (2), and dripping the part of the photo-cathode coated with 3D-rGO and the photo-anodeTiO having dye adsorbed in the pole2The films were partially overlapped, encapsulated with Surly film at 140 ℃ and compacted.
The technical scheme of the invention achieves the following beneficial technical effects:
1. according to the method for preparing the three-dimensional graphene, GO is dissolved in water to form a brown solution, filtering is carried out, the pH value of filtrate is adjusted to be 10.56 by ammonia water, and the color of the solution is changed into black. And carrying out hydrothermal reaction on the black solution to obtain black precipitated rGO. Centrifuging, washing the solid with water and ethanol, freezing the solid at-20 deg.C overnight to freeze the sample into solid, and freeze drying to obtain 3D-rGO. Freeze-drying can be used for directly sublimating ice in a frozen fixed sample, so that the aim of drying is fulfilled. The 3D-rGO obtained by freeze drying has an obvious cellular hole structure formed among the sheets, and the porous sheets are staggered, so that the original components and structure can be maintained, and the product can become loose and porous, thereby enlarging the specific surface area of a sample. The electrolyte can be fully contacted with a 3D-rGO counter electrode in a counter electrode material of a battery, and I is promoted3 -Reduction of I-The reaction takes place.
2. Electrical property research is carried out through a cyclic voltammetry curve, a Nyquist impedance spectrum and a Tafel polarization curve, and the electrocatalytic activity of the surface 3D-rGO material counter electrode is higher than that of the rGO counter electrode.
3. Obtaining open-circuit voltage (V) by using the prepared 3D-rGO as a quasi-solid electrolyte sensitized cell of a counter electrodeoc) 0.704V, short circuit photocurrent density (J)sc) Is 11.87mA/cm-2The Filling Factor (FF) is 57.6%, the Photoelectric Conversion Efficiency (PCE) is 4.81%, compared with the rGO counter electrode, the photoelectric efficiency is improved by 51.26%, the excellent photoelectric performance is derived from a 3D-rGO three-dimensional structure, and more contact areas are provided for the electrolyte and the electrolyte material.
Drawings
FIG. 13 schematic of the preparation of D-rGO;
FIG. 2 XRD patterns of GO, rGO and 3D-rGO;
FIG. 3A SEM image of rGO; FIG. 3B SEM image of 3D-rGO;
FIG. 4 cyclic voltammograms of rGO and 3D-rGO;
FIG. 5 Nyquist impedance Spectroscopy for symmetrical cells assembled with rGO and 3D-rGO
FIG. 6 polarization curves for rGO and 3D-rGO
FIG. 7J-V curves for electrode sensitized cells based on rGO and 3D-rGO.
Detailed Description
First, experimental part
1. Synthesis of three-dimensional graphene
Weighing 40mg of Graphene Oxide (GO) into a beaker, adding 100mL of distilled water, performing ultrasonic treatment until the GO is completely dissolved, adding ammonia water to adjust the pH value to 10-11, transferring the mixed solution to a reaction kettle, and performing hydrothermal reaction at 180 ℃ for 20 hours, as shown in figure 1. And cooling to room temperature to obtain a black reduced graphene oxide (rGO) solid, and centrifuging and washing for four times, wherein each time is 20 min. After centrifugation, the mixture is firstly frozen overnight at the temperature of minus 20 ℃, and then is frozen and dried for 60 hours in a freeze dryer, so that the three-dimensional graphene (3D-rGO) can be obtained.
2. Battery packaging
Manufacturing a photo-anode: placing cleaned FTO glass of 3cm × 6cm on screen printer with conductive surface facing upward, and uniformly coating TiO on scraper2Slurry, scraper inclined at 45 deg., brush with downward force, TiO2The slurry permeates into the FTO glass through the small holes on the template, so that a layer of TiO is uniformly brushed on the conductive surface of the FTO glass2Placing the brushed FTO glass in a muffle furnace, heating the muffle furnace to 500 ℃ within 1h, preserving the heat at 500 ℃ for 1h, and taking out after cooling; repeating the steps for 3 times until 3 layers of uniform TiO are brushed on the same position of the FTO glass2The film thickness is 13 μm.
Will be brushed with TiO2The conductive glass is heated for 1h at 140 ℃, and is put into a prepared N719 dye solution (3mg of N719 dye is dissolved in a mixed solvent of 5mL acetonitrile and 5mL tert-butyl alcohol) to be soaked for 16-18h while the conductive glass is hot, and the conductive glass is taken out, washed for 3-4 times by acetonitrile and dried for standby.
Manufacturing a photocathode: preparing 0.4mg/mL three-dimensional graphene (V)Anhydrous ethanol:VUltrapure water2:1) suspension, absorbing and preparing 3D-rGO solution by using a liquid transfer gun, and coating the solution on the surface of the adhesive tapeAnd (3) in a square shape (because the three-dimensional graphene has an agglomeration phenomenon, 5 mu L of solution is firstly absorbed for dripping), the solution is dried under an infrared lamp, the dripping is continued after the solution is dried, and the step is repeated until a layer of thin material is arranged on the FTO glass, the 10 mu L of solution is absorbed again, and the total dripping is 120 mu L. After the solution is dried, the adhesive tape is torn off, and the solution is put into a tube furnace to be sintered for 1h at 200 ℃ under nitrogen atmosphere.
Packaging of the battery: taking a TiO block absorbed with dye2Conductive glass (photo anode) and a piece of porous conductive glass (photo cathode) coated with 3D-rGO solution, a part coated with 3D-rGO and TiO adsorbed with dye2The films were partially overlapped, encapsulated with Surly film at 140 ℃ and compacted.
Second, result and discussion
1. Synthesis of 3D-rGO
GO is dissolved in water to form a brown solution, the brown solution is filtered, the pH value of the filtrate is adjusted to 10.56 by ammonia water, and the solution becomes black. And carrying out hydrothermal reaction on the black solution to obtain black precipitated rGO. Centrifuging, washing the solid with water and ethanol, freezing the solid at-20 deg.C overnight to freeze the sample into solid, and freeze drying to obtain 3D-rGO. Freeze-drying can be used for directly sublimating ice in a frozen fixed sample, so that the aim of drying is fulfilled. The 3D-rGO obtained by freeze drying not only can keep the original components and structure, but also can make the product become loose and porous, thereby enlarging the specific surface area of the sample.
2. Structure and morphology of 3D-rGO
FIG. 2 gives the XRD patterns of GO, rGO and 3D-rGO. The index of PDF2 is obtained according to the diffraction mode, and in the diffraction pattern of GO, a characteristic peak appears near 10.61 degrees 2 theta, which is the diffraction peak of the (001) crystal face of graphite oxide. When the graphene oxide is reduced, a wider diffraction peak appears at about 25 degrees 2 theta in the rGO map, and is a (002) crystal face diffraction peak of the graphene. This indicates that during the reduction process GO loses most of the oxygen containing groups resulting in a decrease in interplanar spacing. In addition, the XRD pattern of the 3D-rGO obtained by freeze drying shows a characteristic peak similar to that of rGO at 2 theta of about 25 degrees. This indicates that the reduced graphene oxide after freeze-drying and hydrothermal treatment only changes the morphology to increase the surface area and does not change the crystal structure.
Morphological features of rGO and 3D-rGO were analyzed by SEM. As can be seen from fig. 3(a), GO is directly reduced to rGO, and the morphology is a corrugated irregular arrangement. By freeze-drying the treated rGO, it can be clearly seen in fig. 3(B) that distinct cellular void structures are formed between the 3D-rGO flakes, and the porous flakes are interlaced to form three-dimensional graphene. The unique structure enables the 3D-rGO to have larger specific surface area, and the electrolyte can be fully contacted with the 3D-rGO counter electrode in the counter electrode material of the battery, thereby promoting I3 -Reduction of I-The reaction takes place.
3. 3D-rGO electrocatalytic activity
(1) Cyclic voltammetric curve testing
A1 cm × 1cm square is formed by attaching an adhesive tape to a 1cm cleaned rectangular conductive glass, and a three-dimensional graphene solution is dropped into the square. Sucking 20 μ L at a time, drying under infrared lamp, repeating dripping and drying after the solution is dried, and dripping 330 μ L. And finally, putting the electrode into a tube furnace under nitrogen atmosphere at 200 ℃ for burning for 1h, cooling to room temperature, taking out, and plating a lead on the other end of the electrode by using indium for later use, wherein the electrode is a working electrode of a three-electrode system. The Pt wire is used as a counter electrode, and the Ag/AgCl is used as a reference electrode. The electrolyte system was 10mM LiI,0.1M LiClO4,1mM I2The scanning speed is 100mV s-1.
Cyclic voltammetry is an important means to evaluate the electrochemical activity and overall performance of electrode materials. Here, a three-electrode system is adopted, namely FTO of counter electrode material is used as a working electrode, Pt wire is used as a counter electrode, Ag/Ag+As a reference electrode, the electrolyte was 10 mLiI, 1 mMII2，0.1M LiClO4. Cyclic voltammograms were measured as shown in figure 4. According to the mechanism of the electrode reaction of DSSCs. In the CV curve of the counter electrode material, the first oxidation-reduction peak is I3 -+2e-＝3I-The second redox peak is 3I2+2e-＝2I3 -The reaction process of (1). As the main function of the DSSCs in the counter electrode catalysis process is catalytic reductionI3 -. Therefore, the first redox peak is the focus of the study. In addition, the peak-to-peak distance E between the first pair of redox peaksppAnd peak current density, where E is an important parameter for measuring the catalytic ability of the electrodeppSmaller values indicate higher catalytic activity of the electrode material; the larger the peak current, the better the catalytic performance of the corresponding material. Only one pair of oxidation peak reduction peaks appear in CV of rGO, no first reduction peak appears, and E is shownppLarger, indicating lower catalytic activity of the material. However, two distinct pairs of redox peaks (E) were present in the CV of 3D-rGOpp0.59V) and peak current significantly greater than rGO, which fully accounts for 3D-rGO material counter electrode catalytic reduction I3 -Has a higher catalytic activity than the rGO counter electrode.
(2) Nyquist impedance Spectroscopy (EIS)
Prepared counter electrode pair I for further evaluation3 -The results of the Nyquist impedance spectroscopy (EIS) of the counter electrode using the symmetrical cell having the structure "counter electrode/electrolyte/counter electrode" of (1) are shown in fig. 5. In the Nyquist diagram, there are two semicircles, the semicircle in the high-frequency region being the charge transfer resistance R of the counter electrode/electrolyte interfacect. Low frequency region semi-circle is electrolyte internal I3 -/I-Nernst diffusion resistance (Z) of an electric pairN). The intercept of the start point of the Nernst diagram in the high-frequency region real axis (Z') is the series resistance R between the cell conductive substrate FTO and the counter electrodes. The associated fit data are shown in table 1.
TABLE 1 parameters and electrochemical data for impedance map fitting
| CE | Rs/Ω | Rct/Ω | ZN/Ω | Epp/V |
| rGO | 2.3 | 34.3 | / | / |
| 3D-rGO | 9.1 | 5.3 | 9.0 | 0.59 |
From FIG. 5 and the table, the R of 3D-rGO can be seenct5.3 omega, the impedance value is much smaller than rGO (R)ct34.3 Ω), indicating that 3D-rGO catalytic activity is higher. The 3D-rGO has a honeycomb structure and a large surface area, can be used as a charge transmission path to improve the conductivity of the 3D-rGO and further provides more active sites to participate in catalytic reaction, so that the 3D-rGO has higher catalytic activity. However, diffusion resistance Z when 3D-rGO is the counter electrodeNLarger than the rGO electrode, probably due to electrolyte I3 -/I-The diffusion rate of 3D-rGO in a honeycomb structure, however, the total resistance (R) of the 3D-rGO electrodes、RctAnd ZNThe sum of) was 23.4 Ω. And no Z is present in rGO electrodeNR of whichsAnd RctThe sum is 36.6 omega, which is obviously larger than the total resistance of 3D-rGO, which has adverse effect on the filling factor of DSSCs, thereby reducing the photoelectric conversion efficiency.
(3) Tafel polarization curve
The Tafel polarization curve is mainly divided into a polarization region (in the low voltage region), a Tafel region (in the middle voltage region), and a diffusion region (in the high voltage region). The slope of the Tafel region can represent the catalytic activity of the material, and when the slope is larger, the electrode made of the material has higher exchange current density, which indicates that the catalytic activity is higher. This experiment is at-1.0V-1.0V voltage range, to the polarization curve of rGO and 3D-rGO electrode test, can see in figure 6 that the slope that Tafel district 3D-rGO negative pole is propped up is greater than the slope that rGO negative pole was propped up, show that 3D-rGO has the exchange current density that is higher than when rGO is as the counter electrode when being regarded as the counter electrode, so 3D-rGO is high in the electro-catalytic activity in catalytic reaction, and this is unanimous with the result of cyclic voltammetry curve and EIS curve.
4. Photovoltaic performance testing
Fig. 7 is a J-V curve obtained for a quasi-solid electrolyte sensitized cell with rGO and 3D-rGO as counter electrodes. Table 2 gives the corresponding performance parameters. As can be seen from the graph and table data, the open circuit voltage (V) was obtained for the cell with 3D-rGO as the counter electrodeoc) 0.704V, short circuit photocurrent density (J)sc) Is 11.87mA/cm-2The Fill Factor (FF) was 57.6%, and the Photoelectric Conversion Efficiency (PCE) was 4.81%. Compared with the photoelectric performance parameters obtained by the rGO serving as the counter electrode sensitized cell, the open-circuit photovoltage, the current density and the filling factor are respectively increased by 8.14%, 22.50% and 14.29%, and the photoelectric efficiency is improved by 51.26%. The excellent photoelectric property is derived from the three-dimensional structure of 3D-rGO, and more contact areas are provided for the contact of electrolyte and an electrolytic material. This is consistent with the results of electrochemical impedance, cyclic voltammetry and polarization curves.
TABLE 2 photoelectric Properties of rGO and 3D-rGO as counter electrode DSSCs
| CE | Voc/V | Jsc/mA cm-2 | FF/％ | PCE/％ |
| rGO | 0.651 | 9.69 | 50.4 | 3.18 |
| 3D-rGO | 0.704 | 11.87 | 57.6 | 4.81 |
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications are possible which remain within the scope of the appended claims.
Claims (10)
1. A synthesis method of honeycomb three-dimensional graphene is characterized in that graphene oxide GO is weighed in a beaker, distilled water is added for ultrasonic treatment until GO is completely dissolved, ammonia water is added for pH adjustment, a mixed solution is transferred to a reaction kettle, and hydrothermal reaction is completed; cooling to room temperature to obtain black reduced graphene oxide rGO solid, and centrifuging and washing; after centrifugation, firstly freezing treatment is carried out, and then freeze drying is carried out in a freeze dryer, so that the three-dimensional graphene 3D-rGO can be obtained.
2. The synthesis method of the cellular three-dimensional graphene according to claim 1, wherein 40mg of graphene oxide GO is weighed in a beaker, 100mL of distilled water is added for ultrasonic treatment until the GO is completely dissolved, ammonia water is added for adjusting the pH value to 10-11, the mixed solution is transferred to a reaction kettle, and the hydrothermal reaction is carried out for 20 hours at 180 ℃; cooling to room temperature to obtain black reduced graphene oxide rGO solid, and centrifuging and washing for four times, wherein each time is 20 min; after centrifugation, the mixture is firstly frozen overnight at the temperature of minus 20 ℃, and then is frozen and dried in a freeze dryer for 60 hours, so that the three-dimensional graphene 3D-rGO can be obtained.
3. The application of the cellular three-dimensional graphene in the quasi-solid dye-sensitized solar cell is characterized by comprising the following steps:
(1) manufacturing a photo-anode;
(2) fabricating a photocathode using the three-dimensional graphene 3D-rGO prepared according to any one of claims 1-2;
(3) and (5) packaging the battery.
4. The application of the cellular three-dimensional graphene in the quasi-solid dye-sensitized solar cell according to the claim 3, wherein in the step (1):
(1-1) putting cleaned 3cm x 6cm FTO glass on a screen printer with the conductive surface facing upwards, and uniformly coating TiO on a scraper2Slurry, inclined scraper, downward force brush, TiO2The slurry permeates into the FTO glass through the small holes on the template, so that a layer of TiO is uniformly brushed on the conductive surface of the FTO glass2Heating the brushed FTO glass in a muffle furnace, and taking out after cooling; repeating the steps for 3 times until 3 layers of uniform TiO are brushed on the same position of the FTO glass2The film is thin, and the thickness of the film is 13 mu m;
(1-2) brushing with TiO2The conductive glass is heated, is put into the prepared N719 dye solution to be soaked when the conductive glass is hot, is taken out, is washed by acetonitrile, and is dried for standby.
5. The synthesis method of the cellular three-dimensional graphene and the application of the cellular three-dimensional graphene in the quasi-solid dye-sensitized solar cell according to claim 4,
in the step (1-1), the inclination angle of the scraper is 45 degrees; the heating conditions in the muffle furnace are as follows: the muffle furnace was warmed to 500 ℃ over 1h and held at 500 ℃ for 1 h.
6. The synthesis method of the cellular three-dimensional graphene and the application of the cellular three-dimensional graphene in the quasi-solid dye-sensitized solar cell according to claim 4,
in the step (1-2), brush with TiO2The conductive glass is heated for 1h at 140 ℃; soaking in prepared N719 dye solution for 16-18 hr; washing with acetonitrile for 3-4 times;
the preparation method of the N719 dye solution comprises the following steps: 3mg of N719 dye was dissolved in a mixed solvent of 5mL acetonitrile and 5mL t-butanol.
7. The application of the honeycombed three-dimensional graphene in the quasi-solid dye-sensitized solar cell according to the claim 3 is characterized in that in the step (2):
preparing a three-dimensional graphene 3D-rGO turbid liquid, sucking the prepared 3D-rGO turbid liquid by using a liquid transfer gun, coating the liquid in a square pasted by an adhesive tape, drying the liquid under an infrared lamp, continuously dripping the liquid after the solution is dried, and repeating the dripping until a layer of thin material is arranged on the FTO glass; after the solution is dried, the adhesive tape is torn off, and the adhesive tape is put into a tube furnace for sintering under nitrogen atmosphere.
8. The application of the cellular three-dimensional graphene in the quasi-solid dye-sensitized solar cell according to claim 7, wherein the preparation method of the three-dimensional graphene 3D-rGO suspension comprises the following steps: the solvent is in a volume ratio VAnhydrous ethanol:VUltrapure waterA mixed solution of 2:1 anhydrous ethanol and ultrapure water, wherein the solute is the three-dimensional graphene 3D-rGO prepared according to any one of claims 1 to 2, and the solute and the solvent are mixed to obtain a 0.4mg/mL three-dimensional graphene suspension.
9. The synthesis method of the cellular three-dimensional graphene and the application of the cellular three-dimensional graphene in the quasi-solid dye-sensitized solar cell according to claim 7 are characterized in that in the process of dripping, 5 μ L of the cellular three-dimensional graphene is sucked for dripping in the first dripping, the second dripping is started to be increased to 10 μ L of the cellular three-dimensional graphene for dripping, and the total dripping is 120 μ L; sintering for 1h in a tube furnace at 200 ℃.
10. The application of the honeycombed three-dimensional graphene in the quasi-solid dye-sensitized solar cell according to the claim 3 is characterized in that in the step (3):
taking the photo-anode manufactured in the step (1) and the photo-cathode manufactured in the step (2), and dripping the part of the photo-cathode coated with 3D-rGO and TiO adsorbed with dye in the photo-anode2The films were partially overlapped, encapsulated with Surly film at 140 ℃ and compacted.
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